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At the core of carbon monoxide dehydrogenase (CODH) active site two metal ions together with hydrogen bonding scheme from amino acids orchestrate the interconversion between CO2 and CO. We have designed a molecular catalyst implementing a bimetallic iron complex with an embarked second coordination sphere with multi‐point hydrogen‐bonding interactions. We found that, when immobilized on carbon paper electrode, the dinuclear catalyst enhances up to four fold the heterogeneous CO2 reduction to CO in water with an improved selectivity and stability compared to the mononuclear analogue. Interestingly, quasi‐identical catalytic performances are obtained when one of the two iron centers was replaced by a redox inactive Zn metal, questioning the cooperative action of the two metals. Snapshots of X‐ray structures indicate that the two metalloporphyrin units tethered by a urea group is a good compromise between rigidity and flexibility to accommodate CO2 capture, activation, and reduction. [ABSTRACT FROM AUTHOR]

Construction of a "net‐zero‐emission" system through CO2 hydrogenation to methanol with solar energy is an eco‐friendly way to mitigate the greenhouse effect. Traditional CO2 hydrogenation demands centralized mass production for cost reduction with mass water electrolysis for hydrogen supply. To achieve continuous reaction with intermittent and fluctuating flow of H2 on a small‐scale for distributed application scenarios, modulating the catalyst interface environment and chemical adsorption capacity to adapt fluctuating reaction conditions is highly desired. This paper describes a distributed clean CO2 utilization system in which the surface structure of catalysts is carefully regulated. The Ni catalyst with unsaturated electrons loaded on In2O3 can reduce the dissociation energy of H2 to overcome the slow response of intermittent H2 supply, exhibiting a faster response (12 min) than bare oxide catalysts (42 min). Moreover, the introduction of Ni enhances the sensitivity of the catalyst to hydrogen, yielding a Ni/In2O3 catalyst with a good performance at lower H2 concentrations with a 15 times adaptability for wider hydrogen fluctuation range than In2O3, greatly reducing the negative impact of unstable H2 supplies derived from renewable energies. [ABSTRACT FROM AUTHOR]

The concept of green carbon science is to promote the goal of achieving carbon neutrality, the importance and urgency of which have been well‐recognized and received worldwide attention. Carbon neutrality has become the focus of research work in many fields, and correspondingly, a growing number of papers and publications have been published over the last few years. However, since carbon neutralization is a real problem that urgently requires technical solutions, the transition from fundamental research to practical applications must be accelerated. A number of research teams are bold in putting things into practice and blazing new trails. This Review summarizes the recent technological developments within the framework of green carbon science, focusing on conducted pilot tests, industrial demonstrations, and commercial applications beyond the laboratory stage. [ABSTRACT FROM AUTHOR]

The electrochemical CO2 reduction (CO2ER) to multi‐carbon chemical feedstocks over Cu‐based catalysts is of considerable attraction but suffers with the ambiguous nature of active sites, which hinder the rational design of catalysts and large‐scale industrialization. This paper describes a large‐scale simulation to obtain realistic CuZn nanoparticle models and the atom‐level structure of active sites for C2+ products on CuZn catalysts in CO2ER, combining neural network based global optimization and density functional theory calculations. Upon analyzing over 2000 surface sites through high throughput tests based on NN potential, two kinds of active sites are identified, balanced Cu−Zn sites and Zn‐heavy Cu−Zn sites, both facilitating C−C coupling, which are verified by subsequent calculational and experimental investigations. This work provides a paradigm for the design of high‐performance Cu‐based catalysts and may offer a general strategy to identify accurately the atomic structures of active sites in complex catalytic systems. [ABSTRACT FROM AUTHOR]

Electrochemical redox‐control is an emerging strategy for the regulation of polymerization process without the addition of external oxidants and reductants, which enables the control over composition, microstructure and properties of the polymer products. In this paper, based on the chemical selectivity of heterometallic Salen‐Co‐Mn complexes of different valences, an electrochemically switchable strategy was developed for the copolymerization of lactide (LA), CO2 and epoxides. The switchable redox reactions endowed this system with the capability to easily synthesize a multi‐block copolymer of polylactide (PLA) and polycarbonate (PC). Moreover, the multi‐block copolymer could be further modified by introducing various monomers with different microstructures and functional groups. [ABSTRACT FROM AUTHOR]

The design of catalysts with high activity, selectivity, and stability is key to the electroreduction of CO2. Herein, we report the synthesis of 3D hierarchical metal/polymer–carbon paper (M/polymer‐CP) electrodes by in situ electrosynthesis. The 3D polymer layer on CP (polymer‐CP) was first prepared by in situ electropolymerization, then a 3D metal layer was decorated on the polymer‐CP to produce the M/polymer‐CP electrode. Electrodes with different metals (e.g. Cu, Pd, Zn, Sn) and various polymers could be prepared by this method. The electrodes could efficiently reduce CO2 to desired products, such as C2H4, CO, and HCOOH, depending on the metal used. For example, C2H4 could be formed with a Faradaic efficiency of 59.4 % and a current density of 30.2 mA cm−2 by using a very stable Cu/PANI‐CP electrode in an H‐type cell. Control experiments and theoretical calculations showed that the 3D hierarchical structure of the metals and in situ formation of the electrodes are critical for the excellent performance. [ABSTRACT FROM AUTHOR]

The controlled electrochemical reduction of carbon dioxide to value added chemicals is an important strategy in terms of renewable energy technologies. Therefore, the development of efficient and stable catalysts in an aqueous environment is of great importance. In this context, we focused on synthesizing and studying a molecular MnIII‐corrole complex, which is modified on the three meso‐positions with polyethylene glycol moieties for direct and selective production of acetic acid from CO2. Electrochemical reduction of MnIII leads to an electroactive MnII species, which binds CO2 and stabilizes the reduced intermediates. This catalyst allows to electrochemically reduce CO2 to acetic acid in a moderate acidic aqueous medium (pH 6) with a selectivity of 63 % and a turn over frequency (TOF) of 8.25 h−1, when immobilized on a carbon paper (CP) electrode. In terms of high selectivity towards acetate, we propose the formation and reduction of an oxalate type intermediate, stabilized at the MnIII‐corrole center. [ABSTRACT FROM AUTHOR]

Abstract: Carbon dioxide (CO2) reduction in aqueous solutions is an attractive strategy for carbon capture and utilization. Cuprous oxide (Cu2O) is a promising catalyst for CO2 reduction as it can convert CO2 into valuable hydrocarbons and suppress the side hydrogen evolution reaction (HER). However, the nature of the active sites in Cu2O remains under debate because of the complex surface structure of Cu2O under reducing conditions, leading to limited guidance in designing improved Cu2O catalysts. This paper describes the functionality of surface‐bonded hydroxy groups on partially reduced Cu2O(111) for the CO2 reduction reaction (CO2RR) by combined density functional theory (DFT) calculations and experimental studies. We find that the surface hydroxy groups play a crucial role in the CO2RR and HER, and a moderate coverage of hydroxy groups is optimal for promotion of the CO2RR and suppression of the HER simultaneously. Electronic structure analysis indicates that the charge transfer from hydroxy groups to coordination‐unsaturated Cu (CuCUS) sites stabilizes surface‐adsorbed COOH*, which is a key intermediate during the CO2RR. Moreover, the CO2RR was evaluated over Cu2O octahedral catalysts with {111} facets and different surface coverages of hydroxy groups, which demonstrates that Cu2O octahedra with moderate coverage of hydroxy groups can indeed enhance the CO2RR and suppress the HER. [ABSTRACT FROM AUTHOR]

Abstract: Electrochemical reduction of carbon dioxide (CO2) into value‐added chemicals is a promising strategy to reduce CO2 emission and mitigate climate change. One of the most serious problems in electrocatalytic CO2 reduction (CO2R) is the low solubility of CO2 in an aqueous electrolyte, which significantly limits the cathodic reaction rate. This paper proposes a facile method of catholyte‐free electrocatalytic CO2 reduction to avoid the solubility limitation using commercial tin nanoparticles as a cathode catalyst. Interestingly, as the reaction temperature rises from 303 K to 363 K, the partial current density (PCD) of formate improves more than two times with 52.9 mA cm−2, despite the decrease in CO2 solubility. Furthermore, a significantly high formate concentration of 41.5 g L−1 is obtained as a one‐path product at 343 K with high PCD (51.7 mA cm−2) and high Faradaic efficiency (93.3 %) via continuous operation in a full flow cell at a low cell voltage of 2.2 V. [ABSTRACT FROM AUTHOR]

Methanol is a very useful platform molecule and liquid fuel. Electrocatalytic reduction of CO2 to methanol is a promising route, which currently suffers from low efficiency and poor selectivity. Herein we report the first work to use a Mo-Bi bimetallic chalcogenide (BMC) as an electrocatalyst for CO2 reduction. By using the Mo-Bi BMC on carbon paper as the electrode and 1-butyl-3-methylimidazolium tetrafluoroborate in MeCN as the electrolyte, the Faradaic efficiency of methanol could reach 71.2 % with a current density of 12.1 mA cm−2, which is much higher than the best result reported to date. The superior performance of the electrode resulted from the excellent synergistic effect of Mo and Bi for producing methanol. The reaction mechanism was proposed and the reason for the synergistic effect of Mo and Bi was discussed on the basis of some control experiments. This work opens a way to produce methanol efficiently by electrochemical reduction of CO2. [ABSTRACT FROM AUTHOR]

It is highly desired to achieve controllable product selectivity in CO2 hydrogenation. Herein, we report light‐induced switching of reaction pathways of CO2 hydrogenation towards CH3OH production over actomically dispersed Co decorated Pt@UiO‐66‐NH2. CO, being the main product in the reverse water gas shift (RWGS) pathway under thermocatalysis condition, is switched to CH3OH via the formate pathway with the assistance of light irradiation. Impressively, the space‐time yield of CH3OH in photo‐assisted thermocatalysis (1916.3 μmol gcat−1 h−1) is about 7.8 times higher than that without light at 240 °C and 1.5 MPa. Mechanism investigation indicates that upon light irradiation, excited UiO‐66‐NH2 can transfer electrons to Pt nanoparticles and Co sites, which can efficiently catalyze the critical elementary steps (i.e. CO2‐to‐*HCOO conversion), thus suppressing the RWGS pathway to achieve a high CH3OH selectivity. [ABSTRACT FROM AUTHOR]